Tintable, dyeable, curable coatings and coated articles

ABSTRACT

The invention disclosed in this application is the use of novel silanes in curable coatings to allow tinting or dyeing of the coatings after they are cured on certain substrates. An example of one such useful silane is   &lt;IMAGE&gt;   The silanes and the curable coatings are also useful as antistat and antifog coatings.

BACKGROUND OF THE INVENTION

This application is a divisional of Ser. No. 340,160, filed Jan. 18,1982, now U.S. Pat. No. 4,421,893.

The present invention relates to coating compositions which are curableand which can be used on transparent solid substrates. These coatingcompositions contain novel silanes which allow for dyeing and/or tinting(hereinafter "tintability") of such solid substrates. The curablecoating compositions, containing the novel silanes, not only allowtintability, but these coating compositions also give excellent abrasionresistance, antifog and antistat properties to the coated article. Inaddition, the coatings described herein give very aestheticallypleasing, uniform, gel-free surfaces to the coated article.

Plastic materials, especially clear, transparent plastic materials, havebeen used in increasing amounts for various applications where the userdesired such properties as lightweightness and ease of handling.Further, plastics have been developed which are not only lightweight butare strong such that they have application in those uses where breaking,cracking or splintering are a problem, such as in eyewear. In the UnitedStates in 1977, the sales of glass spectacle lenses was estimated atabout 40 million pairs as opposed to about 21 million pairs for plastic.It is predicted that in 1982, 30 million pairs of glass lenses will besold as compared to 40 million pair of plastic lenses.

A certain number of these lenses will be tinted in order to reduce thetransmission of light through them. This tintability of the lenses doesnot seem to be a major problem, since there are a number of tints ofvarying colors which can be used to tint the lenses. Moreover, theplastics are readily receptive to these tints so that variousintensities, as well as various colors of lenses, can be obtained.

Plastic substrates have several major problems, however. Generally,polycarbonates and acrylics are soft, and articles prepared from theseplastics scratch or abrade quite readily. Therefore, there has been agreat deal of investigation into coatings for such articles in order toenhance the abrasion resistance of the surface of the plastic articles.This problem is particularly acute in plastic lenses and transparentplastic sheeting used in bus, airplane, and train windows and inarchitectural windows and panels.

One premier coating that has found wide acceptance for such applicationsis the coating known as the Dow Corning abrasion resistant coating,which is a siloxane based, silica reacted, curable coating especiallyadapted to give hard surfaces when cured on plastic substrates. Thismaterial is disclosed in U.S. Pat. No. 3,986,997, issued Oct. 19, 1976.This material, however, even though having a hard, abrasion resistantsurface, has a major drawback. It is not tintable! Therefore, it wouldbe useful to develop an abrasion resistant coating which not only gaveenhanced abrasion resistance to these plastic substrates, but it wouldbe extremely useful if the coating was also tintable.

Such coatings have been developed, but they too have some drawbacks. Forexample, U.S. Pat. No. 4,211,823, issued July 8, 1980, describes thepreparation of a tintable coating for use on plastic substrates. Thematerial comprises a hydrolyzate of a silane compound containing atleast one epoxy group and not less than two alkoxy groups, fine silicaparticles and an aluminum chelate compound. This material is tintablebut suffers from the fact that it is not exceptionally abrasionresistant, and it has a short resin pot life with a tendency to easilyform gel specks.

Another coating system for use on lenses is a material described in U.S.Pat. No. 4,073,967, issued Feb. 14, 1978, as a combination of a reactivesilane and a metal cluster. This material is tintable but does not offerthe ultimate in abrasion resistance and handleability.

Furthermore, it would be desirable to have an additive for variousresins in order to achieve tintability in resins which are notthemselves ordinarily tintable.

The silane adducts of this invention help overcome the problemsassociated with the prior art materials and, in addition, these silaneadducts are not volatile under coating curing conditions or in use inthe cured coating. As long as the silane adducts are compatible with thecurable resin, the adduct will be useful and perform its functiontherein.

THE INVENTION

This invention therefore deals with a composition of matter which is asilane having the general formula (XO)₃ SiRSR' wherein X is an alkylradical of 1-4 carbon atoms, R is a divalent aliphatic hydrocarbonradical containing less than five carbon atoms and R' is selected from agroup consisting of ##STR2## wherein Q is a radical selected from agroup consisting of --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, ##STR3## wherein ingroups (iii), and (iv), R" is hydrogen or the methyl group and in group(ii), R" is hydrogen, the methyl group or the isobutoxymethyl group.

In this invention, X is an alkyl radical of 1-4 carbon atoms, andexamples of such radicals include the methoxy, ethoxy, propoxy andbutoxy radicals. It should be noted that there are always three suchgroups per molecule. It is believed that the presence of these groupsallows for the non-volatility of the compound when heated during thecure reaction or when the cured coating is subjected to extremetemperatures when in use.

R for purposes of this invention is a divalent aliphatic hydrocarbonradical containing less than five carbon atoms. The alkylene bridge inthese silanes should be as small as possible, as the increased molecularsize leads to the loss of abrasion resistance in the final cured resin.Therefore, the alkylene bridge is preferred to be three carbons or lessin length. Thus, methylene, ethylene and propylene radicals are thepreferred alkylene bridges in this invention. Most preferred is thepropylene bridge because of the simplicity of manufacturing the silanesusing the propylene bridge precursor, i.e. the allyl group.

The letter S is a sulfur atom and R' is selected from a very narrowgroup as set forth in the specification above as groups (i)-(v). Q inthese groups is a radical selected from a group consisting of --CH₂ CH₂--, --CH₂ CH₂ CH₂ --, ##STR4##

R" in these groups takes on a different meaning depending on whichgroup, (ii), (iii) or (iv), is being considered. In groups (iii) and(iv), R" can be hydrogen or the methyl group, and in group (ii), R" canbe hydrogen, the methyl group or the isobutoxymethyl group. No suchgroups are shown as required for groups (i) or (v) because of the natureof the molecules.

The limitations on these groups, R", is only because of theunavailability of the precursor compounds.

There are a number of methods by which these materials can be produced.It is known, for example, to add mercaptan groups to unsaturated organicgroups under the influence of free radical catalysts or ultravioletlight. Thus, one can prepare these compounds by addingmercaptoalkyl-containing trialkoxy silanes to unsaturated organic aminesand amides or, one can add mercapto containing organoamines or amides tounsaturated trialkoxysilanes. Conventional free radical catalysts orultraviolet light will cause such reactions to be efficient; however,sometimes added catalysts are not necessarily required for thesereactions. Sometimes solvents can be used, but they are not required insome cases. Generally, the materials to be reacted are mixed togetherand then catalyzed and then gently heated. Quite frequently, aftergentle heating, the reaction exotherms to near completion of thereaction. Occasionally, the reaction is required to be refluxed for aperiod of time to ensure the completion of the addition reaction.

The preferred method for this invention is the addition of commerciallyavailable mercaptoalkyl-containing trialkoxysilanes to unsaturatedorganic amines or amides under the influence of peroxides orazobisisobutyronitrile catalysts. The unsaturation on the organicprecursors is preferred to be the allyl or vinyl groups.

The examples clearly illustrate the methods and means preferred for themanufacture of the inventive silanes herein.

A further aspect of this invention is the use of the above-mentionedsilanes as additives to curable resins. This invention therefore alsoconsists of a composition of matter which comprises

(A) 1 to 50 weight percent, based on the weight of (A) and (B), of asilane having the general formula (XO)₃ SiRSR' wherein X is an alkylradical of 1 to 4 carbon atoms, R is a divalent aliphatic hydrocarbonradical containing less than five carbon atoms and R' is selected from agroup consisting of ##STR5## wherein Q is a radical selected from agroup consisting of --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, ##STR6## wherein ingroups (iii) and (iv), R" is hydrogen or the methyl group and in group(ii), R" is hydrogen, the methyl group or the isobutoxymethyl group and

(B) 99 to 50 weight percent, based on the weight of (A) and (B), of acurable resin compatible with component (A).

The curable resin and the silane additive must be compatible in orderfor the additive to function as it should, to give uniform tintability.Generally, from 1 to 50 weight percent of silane (A), based on the totalweight of (A) and (B), will work properly in this invention. Generally,as the weight percent of the additive in the composition increases, theintensity of the tint increases. Also, as the weight percent of theadditive in the composition increases, the abrasion resistancedecreases. The abrasion resistance will decrease nominally at the loweramounts of additive, i.e., 1-25 weight percent, then the abrasionresistance will decrease dramatically with larger quantities ofadditive. The loss of abrasion resistance is dependent on the curableresin used and the amount of additive used in that resin. Normally,15-35 weight percent of the additive gives the best tintability and theleast amount of loss in abrasion resistance.

The additive is useful in any curable resin in which it is compatible.

Since the additive is a silane, it is quite compatible withsilicone-based resins or silicone-organic resins. It is least compatiblewith organic resins. The additive is highly compatible with the resinsdescribed in U.S. Pat. Nos. 4,073,967, 4,211,823 and 3,986,997, and widevariations of such pigment-free coating compositions. Especially goodresins, which are highly compatible with the additives of thisinvention, are these comprising 30 to 70 weight percent of colloidalsilica; 0 to 25 weight percent of R""SiO_(3/2) as a partial hydrolyzate,wherein R"" has the meaning set forth for R in U.S. Pat. No. 3,986,997and includes also the phenyl radical and the gamma mercaptopropylradical and 15-35 weight percent of the silane additive, all based onthe total weight of colloidal silica, R""SiO_(3/2) and silane additivein the mixture. This material is similar to the compositions describedin U.S. Pat. No. 3,986,997, but the relative amounts of colloidal silicaand partial hydrolyzate are changed to enhance the tintability of filmsprepared from this resin. The amount of partial hydrolyzate can bereduced to zero if the silane additive is cohydrolyzed into the systemalong with the colloidal silica. Small amounts of the partialhydrolyzate can be used with the colloidal silica, that is, up to 25weight percent of the colloidal silica/partial hydrolyzate can bepartial hydrolyzate. The solvents, catalysts and adjuncts set forth inU.S. Pat. No. 3,986,997 can also be used in this resin composition.

It is possible to use solvents to enhance the compatibility of thesilane additive in the resin systems. Solvents found to be useful hereinare alcohols, glycols, glycol ethers, ketones and esters.

Catalysts for these resin systems are dependent on which systems areused. The presence of the silane in the resin does not appear to affectcatalysis.

One further aspect of this invention is a solid substrate coated withthe silane additive. Thus, the silane additive can be made curable and,in this form, it can be coated on a substrate, cured, and be tinted inthe manner described in the examples.

In addition, the invention consists of solid substrates coated with theresin composition containing the silane additive. This aspect of theinvention is very important because of the fact that a storage stable,one coat, tintable, curable coating is needed in the marketplace forplastic spectacle lenses and plastic windows and decorative panels.

Further, the resin compositions containing the silane additives areuseful as coatings on various substrates as an antistatic coating. Thus,this material can be used on any substrate, transparent ornon-transparent, if an antistatic coating is required. Further, thismaterial can be used as an antifog coating on various substrates and,therefore, when an antifog coating is required, this material can beused.

It should be noted that the silane additive can be cured throughhydrolysis and then catalysis so that the silane additive itself can beused as an antistatic and/or antifog coating.

Substrates that can be coated with the compositions of this inventioninclude leather, plastic, wood, metal, rubber, paper and glass.

Particularly, plastic lenses, sheets and art objects can be coated.Glass windows, for example aircraft windows, can be made antifog andantistatic. Metals can be coated with these compositons, especiallyaluminum, which when coated with these compositions, can be tinted withvarious tints and dyes.

In the following examples, the apparatus and testing procedures used forthe results shown therein are as follows:

Vapor Degreasing

Some of the plastic panels used herein were degreased by subjecting themto a five minute immersion in Freon™TES (trichlorotrifluoroethaneincluding 4% denatured ethanol and a stabilizer proprietary to DuPont,E. I. DuPont deNemours, Wilmington, Del., USA) in a Branson UltrasonicDegreaser (Branson Cleaning Equipment Co., Shelton, CT, USA).

Heat Cleaning

After vapor degreasing, all plastic panels coated in the examples wereheat annealed by subjecting the panels to at least two hours at 125° C.for polycarbonate and two hours at 80° C. for acrylic. The panels werealways cooled to room temperature before coating.

Tinting Materials

All tinted samples were tinted using Sun Brown Molecular Catalytic™ dyesmanufactured by Brain Power Inc., Miami, FL, USA.

The samples were tinted in a hot aqueous bath at about 85° C. for 15minutes. The length of time of tinting when varied is noted in theexamples.

Light Transmission

The amount of tintability was determined by reading the amount of lighttransmitted through a coated panel. The difference in light transmissionbefore and after the tinting was taken on a Gardner® Haze Meter, ModelUX10 coupled to a P5500 Photometric Unit. The light transmission isreported in percent of total light transmitted through the sample.

Adhesion Testing

Adhesion was measured by crosscut adhesion. A series of scratches aremade through the coating into the substrate in the pattern of a gridcontaining 25 squares, each being about 1.5 mm square (1/16 in.). Thissurface is covered with No. 600 Scotch Brand adhesive tape (3M C., USA)and pressed down firmly. The tape is withdrawn from the surface with onerapid motion at about a 90° angle from the surface of the substrate. Thenumber of squares remaining intact on the substrate are reported as apercentage of the total number of squares on the grid.

Abrasion Resistance

Abrasion resistance was determined according to ASTM Method D1044-56.The instrument was a Taber Abraser. A 500 gram test load was used withCS-10F abrasive wheels and the test panels were subjected to 500revolutions on the abraser turntable. The percent change in haze whichis the criterion for determining the abrasion resistance of the coatingis determined by measuring the difference in haze of the unabrased andabrased coatings. Haze is defined as the percentage of transmitted lightwhich, in passing through the specimen, deviates from the incident beamby forward scattering. In this method, only light flux that deviatesmore than 2.5 degrees on the average is considered to be haze. The %ΔHaze on the coatings was determined by ASTM Method D1003-61. A HunterHaze Meter, manufactured by Gardner Laboratory, Inc., was used The ΔHaze was calculated by measuring the amount of diffused light, dividingby the amount of transmitted light and multiplying by one hundred.

EXAMPLE 1 Preparation of ##STR7##

Vinylpyrrolidone, 55.6 gms. (0.5 mole) was weighed into a 500 ml.,3-necked, round-bottomed glass flask. The flask was equipped with awater-cooled condenser, stirrer, thermometer, addition funnel and gasinlet tube. Mercaptopropyltrimethoxysilane, 107.8 gms. (0.55 mole) andVazo® 64 catalyst (2,2'-azobis isobutyronitrile manufactured by E. I.DuPont deNemours and Co. Inc., Wilmington, Del., USA) (0.5 gm.) weremixed and placed in the addition funnel. Nitrogen flow was started toremove air from the flask and apparatus and nitrogen purge was usedthroughout the duration of the experiment. The flask was heated to about82° C. and the mixture from the addition funnel was added to the flaskcontents which were reddish-purple in color at the beginning of theaddition. The color turned to clear brown and then to clear yellow. Anexotherm was observed to about 90° C. where it was controlled with anice water bath and the flask temperature was maintained between 85°-90°C. during the reaction. The addition took place over about 1 hour. Thereaction was heated for about four hours after the addition had beenmade. An aliquot of the reaction product was titrated using standardizediodine to show that the anticipated reaction has proceeded to greaterthan 96% completion. Proton NMR analysis showed a structure consistentwith the title compound.

EXAMPLE 2 Preparation of ##STR8##

Mercaptopropyltrimethoxysilane, 107.8 gms., was weighed into a flaskequipped as in Example 1, above. Vazo 64, (0.5 gm.) was added and thesolution stirred to dissolve the Vazo 64. The N,N-dimethylacrylamide(NNDA) was poured into the addition funnel and the flask was heated to80° C. The addition was begun and was accompanied by an exotherm whichwas controlled between 82°-90° C. The addition was made in about 20minutes. The pot temperature was maintained for about four additionalhours after the addition was complete. Iodine titration showed thereaction had proceeded to about 97% conversion. Proton NMR analysisshowed the structure consistent with the title compound.

EXAMPLE 3 Preparation of ##STR9##

Mercaptopropyltrimethoxysilane, 100 gms. (0.5 mole) was weighed into aflask and the flask was equipped as in Example 1 above. To this wasadded 0.6 gm. of Vazo 64. Methacrylamide (MA) 42.6 gms. (0.5 mole) wasdissolved in 150 gms. of methanol and placed in the addition funnel andadded to the flask over a six-hour period while the flask was heated andmaintained at about 85° C. The heat was shut down and the remainder ofthe addition was carried out over a 14-16 hour period. A small amount ofVazo 64 was added to the flask and reheating was started and thetemperature was taken to about 100° C. and held for about six hours.Another small amount of Vazo 64 was added and the temperature was raisedto 105° C. for an additional seven hours. The reaction had proceededabout 86% as indicated by an iodine titration. The H'NMR analysis isconsistent with the structure (CH₃ O)₃ Si(CH.sub. 3)₃ SCH₂CH(CH₃)C═ONH₂.

EXAMPLE 4 Preparation of ##STR10##

Mercaptopropyltrimethoxysilane, 92 gms. was placed in a 500 ml flaskwhich was equipped as in Example 1. Then, 15.8 gms. of the silane wasplaced in a glass vial and there was added 0.5 gm. of Vazo 64 catalyst.The catalyst did not completely dissolve and an additional 2 gms. ofsilane was added to the vial to help dissolve the catalyst. Thereafter,58.1 gms. of allyl thiourea was added to the flask, in toto, and thecatalyst/silane mixture was placed in an addition funnel. The flask washeated to about 85° C. which caused the solid allylurea to melt. TheVazo/silane mixture was then added at a fast dropwise rate whereupon thetemperature dropped rapidly and, at the end of the addition, thetemperature began to increase and it finally reached 95° C. Thetemperature was held at 90°-95° C. for 5 hours. During this time, thereaction material colored from yellow to orange to brown. An iodinetitration showed the reaction had progressed about 42%. Another 0.3 gm.of catalyst was added and the reaction was heated for another 8 hours atabout 90°-95° C. at which time a titration showed the reaction had goneto about 56% completion.

EXAMPLE 5 Preparation of ##STR11##

The reaction was carried out approximately as set forth in Example 1.Mercaptopropyltrimethoxysilane, 105 gms., was reacted with 78.6 gms. ofisobutoxymethylacrylamide by adding the isobutoxymethylacrylamide to thesilane at 100° C. over a period of about 2 hours and then the reactionwas heated an additional 5 hours. A titration indicated that thereaction was 86% complete.

EXAMPLE 6 Preparation of ##STR12##

One hundred grams of mercaptopropyltrimethoxysilane and 0.45 gm. of Vazo64 were placed in a flask equipped as in Example 1 above. The mixturewas heated to 100° C. and vinyl pyridine was added from an additionfunnel (52.5 gms.). The temperature rose to 120° C. whereupon theheating was discontinued and the temperature was reduced to about 100°C. The addition required about 45 minutes. After 21/2 hours of heating,the contents of the flask were golden brown in color. The reaction washeated at 100° C. for about 6 hours. The reaction had proceeded to about96% completion as indicated by a titration for the residual --SH.

The reaction product was analyzed by H'NMR analysis and the analysis wasconsistent with the structure ##STR13##

EXAMPLE 7 Preparation of ##STR14## using a peroxide catalyst as a freeradical source

Into a 500 ml., 3-necked flask equipped as in Example 1, there was added105 gms. of mercaptopropyltrimethoxysilane and 0.5 gm. of benzoylperoxide. Into an addition funnel there was poured 55.6 gms. of vinylpyrrolidone. The flask was heated to about 90° C. and the addition wasbegun. The addition took about one hour and the contents of the flaskcolored from clear yellow to clear yellow brown. After the addition wascomplete, the contents were heated for four additional hours at about90° C. and the contents continued to color a darker brown. An iodinetitration indicated that the reaction had progressed to essentially 100%completion.

EXAMPLE 8 The preparation of ##STR15## without the addition of a freeradical catalyst

Mercaptopropyltrimethoxysilane, 105 gms., was placed in a 500 ml.,3-necked flask and equipped as in Example 1. Vinyl pyrrolidone, 55.6gms., was poured into the addition funnel. The silane was heated to 100°C. and the pyrrolidone was added thereto with an exotherm which wascontrolled to 95°-105° C. over one hour. At the end of this time, aniodine titration indicated the reaction was about 95% complete. Thereaction was heated for about 21/2 additional hours to ensure completionof the reaction.

EXAMPLE 9 Tintability of an abrasion resistant coating using ##STR16##

A commercial abrasion resistant coating resin prepared according toExample 1 of U.S. Pat. No. 3,986,997 and available from Dow CorningCorporation, Midland, Michigan, as Q9-6312 abrasion resistant coatingresin, was used in the following manner with the tintable adductprepared as in Example 1 herein. The tintable adduct at 100% solids wasdiluted with isopropanol/butanol (50/50 weight percent) to 45 weightpercent solids. One hundred grams of this diluted solution was added to400 gms. of the Q9-6312 resin. The pH of the mixture was adjusted to 4.7by the use of acetic acid. A trace of a surfactant was added to help thecoating wet out on the surface.

Three polycarbonate plastic panels (4"×4") were vapor degreased to cleanthem, and then they were heat annealed at 125° C. for two hours in anair circulating oven. The panels were then flow coated with the coatingresin prepared above which contained the tintable adduct and cured in anair circulating oven at 125° C. for 16 hours. The panels were cooled andone panel was tested for adhesion of the coating and for abrasionresistance. Two of the panels were tinted by using a brown dyemanufactured by Brain Power, Inc., Miami, FL, USA, and named Sun Brown.

The dye bath was heated to 95° C. and the panels were immersed in thebath for 15 minutes and removed. The coating dyed a greenish-browncolor. Polycarbonate panels coated with the adduct-modified Q9-6312without tinting have a light transmission of 90.4%. The tinted panel(average of two panels) light transmission was 80.5% or a reduction of10% in light transmission. A sample of the Q9-6312 without the adductwould not tint at all, even on prolonged immersion in the heated dyebath. The adhesion of the coating containing the adduct, before tinting,was 100% and after tinting, the adhesion was still 100%. The % Δ Hazeabrasion reading was 5.5%.

EXAMPLE 10

An abrasion resistant coating resin was prepared according to thegeneral procedure set forth in U.S. Pat. No. 3,986,997. This resincomposition was combined in various proportions with various adducts setforth in Table I such that the final resin composition was about 34%solids, wherein the solids consisted of about 54 weight percent SiO₂, 16weight percent CH₃ SiO_(3/2) and 30 weight percent adduct as thesilsesquioxane i.e. RSiO_(3/2). The pH of all of the resin samples wasadjusted to 4.7 prior to curing on the panels. Polycarbonate panels(4"×4") were flow coated with the resin compositions and cured at 125°C. for 16 hours in an air circulating oven. When removed from the ovenand cooled, Sample 4 panels crazed badly.

The panels were then tinted using the brown dye bath, as in Example 9,for 15 minutes.

The results are on Table I.

                                      TABLE I                                     __________________________________________________________________________    Results of Tinting on Coated Polycarbonate Panels                                                    Tintability                                                                            Abrasion Resistance                           ASiO.sub.3/2 where     % Transmission                                                                         % Δ Haze                                                                          % Adhesion                          Sample No.                                                                          A is --          Pretint                                                                           Posttint                                                                           Pretint                                                                            Posttint                                                                           Pretint                                                                           Posttint                        __________________________________________________________________________    1     No adduct        90.4                                                                              90.4 2.0  2.0  100 100                                                        (No tint-                                                                     ability)                                                  ##STR17##       89.4                                                                              50.2 8.4  9.5  100 100                               3                                                                                  ##STR18##       89.4                                                                              68.3 4.9  4.0   0   0                                4                                                                                  ##STR19##       88.9                                                                              67.3 5.5  3.5   0   0                                5                                                                                  ##STR20##       89.5                                                                              43.9 11.3 6.1  100 100                             __________________________________________________________________________

EXAMPLE 11

This example illustrates the versatility of utility of the adducts ofthis invention in various siloxane resins containing SiO₂. In this case,R in the RSiO_(3/2) is changed to change the type of resin obtained.

The colloidal silica used in this example is a basic colloidaldispersion of 13-14 millimicrons silica (pH 9.8, Na₂ O content of0.32%). The adducts were added as 100% solids reaction products. Sodiumacetate catalyst was also added to the final composition before curingthe resin on the panels.

A base resin is prepared by adding each silane to colloidal silica atweight ratios of 78.5:21.5 SiO₂ to silane. This material is then dilutedwith isopropanol/butanol (IPA/BuOH) solvent (1:1 weight ratio) to obtainthe final composition. One sample will illustrate the procedure.

The silane, in the trialkoxy form, is combined with the aqueouscolloidal silica and mixed while hydrolysis takes place for about 90minutes. The composition is then diluted with IPA/BuOH (2:1 weightratio), and the adduct was added with stirring which was continued fortwo hours after the addition. The catalyst was then added. Each resinwas flow coated onto B 4"×4" polycarbonate panels, air dried and cured16 hours at 125° C. Three panels were coated with each resin. The adductused in each case was that prepared as in Example 1. (See Table II forresin compositions and Table III for results of adhesion and tinting).The dye procedure and bath was the same as used in Example 9.

                                      TABLE II                                    __________________________________________________________________________    Composition Data for Resin Compositions                                                               SiO.sub.2 /                                                                       CH.sub.3 COOH/                                                                       Adduct/                                                                            Solvent/                                                                           Catalyst/                        Ref.                                                                             Silane Type/gms.     gms.                                                                              gms.   gms. gms. gms.                             __________________________________________________________________________    A  Vinyltrimethoxysilane                                                                          (11.8)                                                                            67.9                                                                              1.6    16.8 39.0 1.29                                B                                                                              ##STR21##       (8.7)                                                                             67.9                                                                              1.5    16.8 43.0 1.29                               C                                                                              (CH.sub.3 O).sub.3 Si(CH.sub.2).sub.3 Cl                                                       (9.7)                                                                             67.9                                                                              1.6    16.8 42.0 1.29                             D  (CH.sub.3 O).sub.3 SiCH.sub.3                                                                  (12.8)                                                                            67.9                                                                              1.7    16.8 39.0 1.29                             __________________________________________________________________________

                  TABLE III                                                       ______________________________________                                        Results on Tintability and Adhesion of Various                                Siloxane/SiO.sub.2 Resin                                                      Tintability    Abrasion Resistance                                                                        % Adhesion                                        Ref.  % Transmission                                                                            % Δ Haze                                                                              Pretint                                                                             Posttint                                ______________________________________                                        A     46.9        19.0          100    0                                      B     10.4        25.4          100   --                                      C     23.6        27.6          100   --                                      D     65.0        6.5           100   90                                      ______________________________________                                    

EXAMPLE 12 The effects on adhesion and tintability while varying thequantity of an inventive adduct

Inventive adduct was prepared as in Example 1. This adduct was dilutedwith IPA/BuOH (1:1) to 35 weight percent solids. This material waslabeled "Component A". "Component B" is the commercial abrasionresistant coating referred to earlier in this application as Q9-6312 andis also 35 weight percent solids. These resins were blended to givevarying ratios of A to B. The blends were then coated on polycarbonateplastic panels and tinted. Adhesion, tintability, and abrasionresistance were tested. A mixture of CH₃ COOH and NaOOCCH₃, 50:50 weightratio, was added to adjust pH to 4.7.

    ______________________________________                                                                      CH.sub.3 COOH +                                  Ref.Sample                                                                          gms.Component A                                                                           gms.Component B                                                                           ##STR22##                                      ______________________________________                                        1     10          90          0.2                                             2     20          80          0.4                                             3     30          70          0.6                                             4     40          60          0.8                                             5     50          50          1.0                                             ______________________________________                                    

see Table IV for test results on these materials.

                  TABLE IV                                                        ______________________________________                                        Results of Adhesion/Tintability/Abrasion Resistance of                        Example 12 Resin Compositions                                                 Sample                                                                              Abrasion Resist-                                                                           % Adhesion     Tintability                                 Ref.  ance/% Δ Haze                                                                        Pretint  Posttint                                                                             % Transmission                             ______________________________________                                        1     3.7          100      100    89.0                                       2     7.0          100      100    84.0                                       3     13.8         100      100    64.6                                       4     20.5         100      100    46.4                                       5     37.5         100      100    37.0                                       ______________________________________                                    

EXAMPLE 13 Preparation of (CH₃ O)₃ Si(CH₂)₃ SCH₂ CH₂ CH₂ NHCONH₂

70 grams of mercaptopropyltrimethoxy silane and 35.5 gms. of allylureawere weighed into a flask equipped as in Example 1. The contents of theflask were heated to about 90° C. and 0.3 gm. of Vazo 64 was added. Thetemperature indicated an exotherm to about 145° C. which was controlledback down to about 100° C. for a total of 61/2 hours and it was thencooled. Titration of a sample showed about 71% reaction of themercaptan. The material was filtered. The proton NMR analysis showed astructure consistent with the title compound. There was unreactedallylurea present at less than 25%.

EXAMPLE 14

The following base resin was prepared. Eighty and eight-tenths grams ofcolloidal SiO₂ (as in Example 1); 15.2 grams of CH₃ Si(OCH₃)₃ and 2grams of CH₃ COOH were stirred together for one hour. 86.9 grams ofisopropyl alcohol was added thereto along with 43.4 gms. of butanol.This material was stirred to homogenize and was then split into twoequal quantities. One-half of this resin was combined with 9.8 gms. ofthe material from Example 13. The second one-half was combined with 9.2gms. of the material from Example 6 and after stirring it gelled. A newresin was prepared and combined with ten gms. of the material fromExample 6. About 630 ppm of sodium acetate in an isopropanol solutionwas added to each combination. The combination using the material fromExample 13 was labeled A. The second combination using the material ofExample 6 was labeled B.

A and B were flow coated on separate polycarbonate 4"×4" plastic panelswhich had been previously vapor degreased and heat annealed for twohours at 125° C. and cooled. After coating, the panels were air driedfor about 15 minutes and then cured in an air circulating oven at 125°C. overnight. The panels were dyed using BPI Sun Brown dye at 90°-95° C.for 15 minutes. The results were as follows. A vinyl pyrrolidone adductin the base resin of this example was prepared and was tested asReference C.

    ______________________________________                                        % Adhesion                  % Light                                           Ref.   Pretint Posttint   % Δ Haze                                                                        Transmission                                ______________________________________                                        A      100     100        18.2    74.0 (30 min.                                                                 immersion)                                  B      100     100        44.2    51.0                                        C      100     100        30.0    73.6                                        ______________________________________                                    

EXAMPLE 15 The use of the inventive adduct in a commercial tintablecoating to further reduce the light transmission

A coating resin was prepared as shown in Example 2 of U.S. Pat. No.4,073,967. This resin was divided into two equal portions. The portionthat was used "as prepared" was designated A. The other half of theresin was combined with an adduct analogous to and prepared as inExample 1 in a quantity of 16 weight percent adduct.

These resins were coated on separate 4"×4" polycarbonate panels and airdried about 15 minutes and then cured overnight (about 16 hours) at 85°C. The panels were tinted as in Example 14 above. The Panel A had alight transmission of 35%. Panel B had a light transmission of less than1%.

EXAMPLE 16 Effect of variation in the SiO₂ content of the coating resinon dyeability/tintability

Five resins were prepared in which the SiO₂ content was varied. Theresins were prepared by mixing methyltrimethoxysilane, colloidal silica(as in Example 1), acetic acid and water. After these materials weremixed and homogenized with stirring, a 50/50 weight ratio of isopropanoland butanol solvent was added to the resin. After continued stirring fora few minutes, the resins cleared and they were then stirred for threehours and there was added thereto an adduct prepared as in Example 1 andhaving the same chemical formula. The resins were allowed to standovernight and about 600 ppm sodium acetate was added to each resin as acuring catalyst. The resin formulations can be found in the followingtable. EXAMPLE 16

    ______________________________________                                        The Resin Formulations                                                                                 gms.       gms. gms. Wt.                                  gms.        gms.    Acetic                                                                              gms. Sol- Ad-  %                               Ref. CH.sub.3 Si(OCH.sub.3).sub.3                                                              SiO.sub.2                                                                             Acid  H.sub.2 O                                                                          vent duct SiO.sub.2                       ______________________________________                                        A    60.8        14.7    1.9   21.0 100  20   10                              B    40.6        44.1    1.7   0.0  91.5 20   30                              C    20.3        73.4    1.7   0.0  82.6 20   50                              D    5.1         95.6    2.0   0.0  73.3 20   65                              E    0.0         102.3   2.0   0.0  73.7 20   70                              ______________________________________                                    

These resins were flow coated on separate polycarbonate 4"×4" panelswhich had been vapor degreased and heat annealed at 125° C. and cooledbefore coating. The panels were cured about 16 hours in an airconvection oven at 125° C.

The panels were tinted using the BPI Sun Brown for 15 minutes at 85° C.The results can be found in Table V.

                  TABLE V                                                         ______________________________________                                        Results of the Variability of the                                             SiO.sub.2 Content of the Base Resin                                           Average                                                                       Coating               %        % Transmission                                 Ref. Thickness/μ                                                                           % Δ Haze                                                                           Adhesion                                                                            Pretint                                                                              Posttint                              ______________________________________                                        A    5.0        15.5      100    89.1   85.4                                  B    4.6        9.5       100    89.0   82.3                                  C    4.2        7.4       100    89.0   76.6                                  D    2.9        20.8      100    88.7   64.2                                  E    2.0        23.7      100    88.5   25.0                                  ______________________________________                                    

In base resin coatings which contain colloidal silica, it is apparentthat greater dyeability can be achieved by increasing the amount of SiO₂in the base resin, but it should be observed that at about 65 weightpercent the coatings start to soften.

EXAMPLE 17 Use of the invention adducts in a commercial silicone resin

Three resins were prepared according to Japanese Patent Publication Sho51 (1976)-123280, Example 3 and Comparison Example 1, page 9 of thepublication. The formulations were prepared by simple mixing as shown inthe publication and they had the following formulations:

    ______________________________________                                        (A)    Methyltrimethoxysilane (MTM)                                                                         27    gms.                                             Vinyltrimethoxysilane (VTM)                                                                          38    gms.                                             CH.sub.3 COOH          8     gms.                                             0.02 N HCl             21    gms                                              Na Acetate             0.4   gms.                                      (B)    MTM                    27    gms.                                             VTM                    38    gms.                                             0.02 N HCl             21    gms.                                             CH.sub.3 COOH          8     gms.                                             Na Acetate             0.4   gms.                                              ##STR23##             2.8   gms.                                      (C)    MTM                    27    gms.                                             VTM                    25    gms.                                             CH.sub.3 COOH          8     gms.                                             0.02 N HCl             21    gms.                                             Na Acetate             0.4   gms.                                             *Adduct                13    gms.                                      ______________________________________                                         *The adduct had the same chemical structure as that prepared in Example 1     of this application.                                                     

Polycarbonate panels (4"×4") were vapor degreased and heat annealed at125° C. and cooled before coating. Both acrylic plastic panels(Plexiglas®G product of Rohm and Haas, Philadelphia, PA, USA) andpolycarbonate panels (Lexan® General Electric Co., Plastic Division,Pittfield, Mass., USA) (4"×4") were flow coated, air dried for 25minutes and then cured in an air convection oven, the acrylic panels at80° C. for 16 hours and the polycarbonate panels at 125° C. for 16hours. The panels were all dyed using BPI Sun Brown at 85° C. for 15minutes. The results are on Table VI.

                  TABLE VI                                                        ______________________________________                                        Results from Example 17                                                       % Δ Haze       % Trans-  %                                              Polycarbonate   Acrylic  mission   Adhesion                                   Ref.  (PC)          (AC)     PC   AC   PC   AC                                ______________________________________                                        A     Crazed Badly  25       --   75    0   100                               B     Crazed Badly  25       --   72    0   100                               C     Crazed About 20%                                                                            20       --   59   100  100                                     of Surface Area                                                         ______________________________________                                    

That which is claimed is:
 1. A solid substrate coated with a compositionof matter which is a silane having the general formula (XO)₃ SiRSR'wherein X is an alkyl radical of 1-4 carbon atoms, R is a divalentaliphatic hydrocarbon radical containing less than five carbon atoms andR' is selected from a group consisting of ##STR24## wherein Q is aradical selected from a group consisting of --CH₂ CH₂ --, --CH₂ CH₂ CH₂--, ##STR25## wherein in groups (iii) and (iv), R" is hydrogen or themethyl group and in group (ii), R" is hydrogen, the methyl group or theisobutoxymethyl group.
 2. A solid substrate coated with a composition ofmatter which comprises(A) 1 to 50 weight percent, based on the weight of(A) and (B), of a silane having the general formula (XO)₃ SiRSR' whereinX is an alkyl radical of 1 to 4 carbon atoms, R is a divalent aliphatichydrocarbon radical containing less then five carbon atoms and R' isselected from a group consisting of ##STR26## wherein Q is a radicalselected from a group consisting of --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --,##STR27## wherein in groups (iii) and (iv), R" is hydrogen or the methylgroup and in group (ii), R" is hydrogen, the methyl group or theisobutoxymethyl group, and (B) 99 to 50 weight percent, based on theweight of (A) and (B), of a curable resin compatible with component (A).3. A method of rendering a substrate antistatic by coating saidsubstrate with a composition of matter which is a silane having thegeneral formula (XO)₃ SiRSR' wherein X is an alkyl radical of 1-4 carbonatoms, R is a divalent aliphatic hydrocarbon radical containing lessthan five carbon atoms and R' is selected from a group consisting of##STR28## wherein Q is a radical selected from a group consisting of--CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, ##STR29## wherein in groups (iii) and(iv), R" is hydrogen or the methyl group and in group (ii), R" ishydrogen, the methyl group or the isobutoxymethyl group.
 4. A method ofrendering a substrate antistatic by coating said substrate with acomposition of matter which comprises(A) 1 to 50 weight percent, basedon the weight of (A) and (B), of a silane having the general formula(XO)₃ SiRSR' wherein X is an alkyl radical of 1 to 4 carbon atoms, R isa divalent aliphatic hydrocarbon radical containing less than fivecarbon atoms and R' is selected from a group consisting of ##STR30##wherein Q is a radical selected from a group consisting of --CH₂ CH₂ --,--CH₂ CH₂ CH₂ --, ##STR31## wherein in groups (iii) and (iv), R" ishydrogen or the methyl group and in group (ii), R" is hydrogen, themethyl group or the isobutoxymethyl group, and (B) 99 to 50 weightpercent, based on the weight of (A) and (B), of a curable resincompatible with component (A).
 5. A method of inhibiting fog on asubstrate by coating said substrate with a composition of matter whichis a silane having the general formula (XO)₃ SiRSR' wherein X is analkyl radical of 1-4 carbon atoms, R is a divalent aliphatic hydrocarbonradical containing less than five carbon atoms and R' is selected from agroup consisting of ##STR32## wherein Q is a radical selected from agroup consisting of --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, ##STR33## wherein ingroups (iii) and (iv), R" is hydrogen or the methyl group and in group(ii), R" is hydrogen, the methyl group or the isobutoxymethyl group. 6.A method of inhibiting fog on a substrate by coating said substrate witha composition of matter which comprises(A) 1 to 50 weight percent, basedon the weight of (A) and (B), of a silane having the general formula(XO)₃ SiRSR' wherein X is an alkyl radical of 1 to 4 carbon atoms, R isa divalent aliphatic hydrocarbon radical containing less then fivecarbon atoms and R' is selected from a group consisting of ##STR34##wherein Q is a radical selected from a group consisting of --CH₂ CH₂ --,--CH₂ CH₂ CH₂ --, ##STR35## wherein in groups (iii) and (iv), R" ishydrogen or the methyl group and in group (ii), R" is hydrogen, themethyl group or the isobutoxymethyl group, and (B) 99 to 50 weightpercent, based on the weight of (A) and (B), of a curable resincompatible with component (A).